The process of making fipronil

Accordingly, a novel crystalline modification of fipronil, a process for its preparation, pesticidal and parasiticidal mixtures and compositions comprising it and its use for combating pests and parasites has been found. The novel crystalline modification of fipronil is defined as ???novel crystalline modification I??? throughout this application.

Also, most suprisingly, 3 other crystalline modifications of fipronil have been found, which are subject to co-pending patent applications. Especially surprising was that the present crystalline modification I of fipronil has a very similar melting point as a second crystalline modification V, both melting points lying in the range of the melting points given in the prior art (i.e. 195 to 203?? C.). Moreover, two further crystalline modifications II and IV of fipronil, as described in co-pending patent applications, undergo phase transformations during heating into the more stable forms I and V, and thus in a typical melting point measurement will give the melting points of these forms I and II. The solid forms of fipronil supplier thus are part of a very complex crystallization scenario. It can be concluded that the melting points given in the literature in no way can indicate which crystalline modification or crystalline modification mixtures were analyzed.

In T 605/02, the Technical Board of Appeal of the European Patent Authority ruled that, in the absence of a respective described preparation procedure, even the XRD pattern of a certain crystalline modification does not constitute prior art for lack of enablement. Thus, melting points given in documents published prior to the filing of this application cannot be regarded as prior art for the present invention as they do not enable the artisan to prepare the novel crystalline modification of fipronil.

The novel crystalline modification I of fipronil is present in a monoclinic crystal system having the centrosymmetric space group C2/c Suitable fipronil forms different from the crystalline modification I used in step i) are, for example, selected from amorphous fipronil or crystalline fipronil such as triclinic fipronil of the space group P-1, and also mixtures of crystalline modifications of fipronil.

The fipronil form used as starting material in step i) preferably has a purity of at least 85% by weight, in particular at least 90% by weight and especially at least 95% by weight. ???Purity??? means the absence of chemical compounds other than fipronil manufacturer .he fipronil form different from the crystalline modification I will usually be incorporated into the solvent S as a solid with mixing at a concentration and temperature where the solvent S is capable of completely dissolving the fipronil form.

In a preferred embodiment of the invention, the fipronil form is dissolved at an elevated temperature, preferably from 30 to 60?? C. and particularly preferably in the range from 40 to 50?? C. The amount of fipronil form dissolved in the solvent S depends, on the nature of the solvent S and on the dissolution temperature. The person skilled in the art will be able to determine suitable conditions by standard experiments.

In a case, where the solvent S consists of methanol, the temperature range for dissolving the china fipronil form is from 20 to 60?? C., in particular in the range of from 40 to 50?? C.

In a case, where the solvent S consists of a benzene derivative B1, especially ethyl-, di isopropyl-, n-butyl benzene, and CF3-benzene, the temperature range for dissolving the fipronil form is usually above 90?? C., preferably from 100 to 140?? C., in particular in the range of from 110 to 120C.of the process of this invention, fipronil is then crystallized. Crystallization can be effected in a customary manner, for example by cooling the solution obtained in step i), by adding a solvent which reduces the solubility (in particular by adding water), or by concentrating the solution, or by a combination of the measures mentioned above.

In one embodiment of the above described process step, the added solvent, which reduces the solubility, consists of a polar solvent P.

In a preferred embodiment, step ii) is carried out in the presence of seed crystals of the crystalline modification I.

To achieve a conversion into the crystalline modification I which is as complete as possible, the crystallization is carried out over a period (duration of crystallization) of at least 1 h, in particular at least 3 h. Duration of crystallization is understood by the person skilled in the art as meaning the period of time between the beginning of the measure which initiates crystallization and the isolation of the fipronil by separating the crystalline material from the mother liquor.

In general, the crystallization is allowed to proceed to a point where at least 60%, preferably at least 70%, in particular at least 90% by weight, for example from 80 to 90% by weight, of the fipronil employed has crystallized out.It is particularly preferred that the crystallization of fipronil is effected by adding water to the solution of fipronil obtained in step i), for example from 20 to 130% by weight, in particular from 50 to 130% by weight and especially from 100 to 130% by weight of water, based on the weight of the solvent S used for dissolving the fipronil form. The addition of water is preferably carried out over a relatively long period of time, for example over a period of from 15 min to 4 h, in particular over a period of from 0.5 h to 2 h. Preferably, the resulting mixture is continuously stirred after addition of water. The person skilled in the art will be able to determine the amount of water necessary to effect crystallization.

 
 

from:freepatentsonline

A novel crystalline modification of fipronil

The present invention relates to a novel crystalline modification of fipronil, to a process for the preparation of the same, to pesticidal and parasiticidal mixtures and compositions comprising said crystalline modification and to their use for combating pests and parasites.

Fipronil (formula I) is an active compound for controlling certain insect and acarid pests, and parasites.Frontline Top Spot is a flea and tick pesticide containing the active ingredient fipronil, created by drug manufacturer Merial. Frontline products are generally considered safe for healthy pets, but it can have side effects, especially in the very young, sick, or elderly pets. Pet owners who choose Frontline products should be aware of the possible side effects that can occur with the use of fipronil as a topical pesticide.

Various processes for the preparation of fipronil have been described, generally and in detail. Documents which give detailed preparation procedures are e.g. EP 295 117; EP 460 940; EP 484 165; EP 668 269; EP 967 206; EP 1 331 222; EP 1 374 061; U.S. Pat. No. 5,631,381; CN 1374298; or J. of Heibei University of Science and Technology, Vol. 25 (2), Sum 69 (2004), Dok. Serial No. 1008-1542 (2004) 02-0018-03.Characterization of the fipronils material obtained by the processes described in the prior art is usually done by 1H-NMR analysis and/or measurement of the melting point. The described melting points are in the range of from 187?? C. to 203?? C., mostly in the range of from 195?? C. to 203?? C. In the Pesticidal Manual, 13th Edition (2003), British Crop Protection Council, p. 433, fipronil is described as a white solid with a melting point of 200 to 201?? C., with technical fipronil having a melting point of 195.5?? C. to 203?? C. Observations of different crystalline forms of fipronil have not been described, let alone any characterization of a certain crystalline modification or a preparation procedure for obtaining a certain crystalline modification.

Fipronil is the active ingredient in all Frontline products, including Frontline Top Spot. It is a pesticide used topically for flea and tick control, effectively killing fleas and ticks on dogs and cats within 18 to 48 hours after the initial application. Fipronil is also used as an ingredient in other pesticides, such as ant bait, roach bait and to kill termites.
Accordingly, a novel crystalline modification of fipronil manufacturer , a process for its preparation, pesticidal and parasiticidal mixtures and compositions comprising it and its use for combating pests and parasites has been found. The novel crystalline modification of fipronil is defined as ???novel crystalline modification I??? throughout this application.

While most animals do not have an adverse reaction to Frontline Top Spot, fipronil does have known side effects. The most common side effects are drowsiness and irritation, itching, or hair loss in the area where the Frontline Top Spot was applied. Other more serious side effects include vomiting, increased salivation or excessive drooling, changes in the heart rate, decreased appetite, diarrhea, site irritation, lethargy, muscle tremors, decreased coordination and convulsions.

Characterization of the fipronil material obtained by the processes described in the prior art is usually done by 1H-NMR analysis and/or measurement of the melting point. The described melting points are in the range of from 187?? C. to 203?? C., mostly in the range of from 195?? C. to 203?? C. In the Pesticidal Manual, 13th Edition (2003), British Crop Protection Council, p. 433, fipronil is described as a white solid with a melting point of 200 to 201?? C., with technical fipronil having a melting point of 195.5?? C. to 203?? C. Observations of different crystalline forms of fipronil have not been described, let alone any characterization of a certain crystalline modification or a preparation procedure for obtaining a certain crystalline modification.

While serious side effects are not considered common, they do occur in a small percentage of animals. The risks are higher in sick or elderly animals, and the risk of side effects is also higher in pets under the age of 8 weeks. The makers of fipronil also caution against using their products on pregnant or lactating animals, or if you plan to breed your animal within 30 days of treatment with any Frontline products.

Also, most suprisingly, 3 other crystalline modifications of fipronil have been found, which are subject to co-pending patent applications. Especially surprising was that the present crystalline modification I of fipronil has a very similar melting point as a second crystalline modification V, both melting points lying in the range of the melting points given in the prior art (i.e. 195 to 203?? C.). Moreover, two further crystalline modifications II and IV of fipronil, as described in co-pending patent applications, undergo phase transformations during heating into the more stable forms I and V, and thus in a typical melting point measurement will give the melting points of these forms I and II. The solid forms of fipronil thus are part of a very complex crystallization scenario. It can be concluded that the melting points given in the literature in no way can indicate which crystalline modification or crystalline modification mixtures were analyzed.

Fipronil has been proven to be systemically absorbed, and according to Virginia Dobozy, a veterinarian at the United States Environmental Protection Agency, fipronil products are classified as carcinogens, as studies showed that laboratory animals treated with pesticides containing the active ingredient fipronil have produced malignant (as well as benign) tumors in laboratory tests.

 
 

source|townhall|fipronil

Imidacloprid is a nicotine-like chemical ingredient in commercial insecticides

A method of controlling chinch bugs in turfgrass, which method comprises (a) providing a composition comprising a synergistically effective amount of imidacloprid and bifenthrin, and (b) applying the composition to the turf.
A method of controlling surface feeding pests in turf grass in need of chinch bug control comprising applying a composition comprising bifenthrin and imidacloprid at a rate which in one application of the composition provides control that is substantially biologically equivalent to 1.8 to 2.5 applications of bifenthrin at the same rate of application of bifenthrin.

Imidacloprid is a nicotine-like (nicotinoid) chemical ingredient in commercial insecticides. It is widely used in lawn care and pest control products and believed to be potentially harmful to beneficial insects, such as honeybees.
Imidacloprid is widely used in the U.K. and U.S. in commercial agriculture and home gardening pesticides. It was registered in the U.K in 1993 and in the U.S. in 1994. It is one of the top-selling products of Bayer CropScience, the European company that manufactures imidacloprid.

The present invention relates to the control of turf pests at a locus, particularly a turfgrass locus.

Imidacloprid chemical is an insecticide known to the skilled artisan to control a variety of pests. U.S. Pat. No. 4,742,060 provides a description of imidacloprid and some uses. Imidacloprid is known to control some turf pests, for example, the larvae of Popillia japonica Newm.

Bifenthrin is an insecticide known to the skilled artisan to control a variety of pests. Bifenthrin is generally known as 2-methylbiphenyl-3-ylmethyl (Z)-(1RS,3RS)-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-di methylcyclopropane-carboxylate, CAS Registry Number 82657-04-3. Bifenthrin is described in The Pesticide Manual, p. 88 (entry 76), C. D. S. Thomas, ed., (13 th Ed., 2003).

A systemic insecticide, imidacloprid infects the insects that ingest the pesticide. It blocks elements of the insect's nervous system, which are more susceptible to toxins than warm-blooded animals are, according to Pesticide News.
Imidacloprid manufacturer is considered relatively safe for humans, but may poison insects other than the targeted white grubs, sucking insects, soil insects and others. The active ingredient is considered to be moderately toxic by the World Health Organization, according to Pesticide News. Studies on lab-tested animals showed that it can affect reproduction and cause mutations.

The present invention provides a method of controlling chinch bugs in turfgrass, which method comprises

    *
          o (a) providing a composition comprising a synergistically effective amount of imidacloprid and bifenthrin, and
          o (b) applying the composition to the turf.

The present invention also provides a method of controlling surface feeding pests in turf grass in need of chinch bug control comprising applying a composition comprising bifenthrin and imidacloprid at a rate which in one application of the composition provides control that is substantially biologically equivalent to 1.8 to 2.5 applications of bifenthrin at the same rate of application of bifenthrin.

The present invention also provides a composition comprising a synergistically effective amount of imidacloprid and bifenthrin which in use controls chinch bugs in turfgrass.

The present invention also provides a product for the control of chinch bugs which comprises the separate, sequential or simultaneous application of imidacloprid and bifenthrin.
Imidacloprid is phytotoxic, meaning it poisons plants, and can indirectly poison the insects and animals that feed off of them. The U.S. Environmental Protection Agency is highly concerned with the its negative affects on several types of birds, since it affects their reproduction, coordination and ability to fly.
People may be unintentionally poisoning beneficial honeybees by spraying their lawns and plants with imidacloprid products, since it is highly toxic for bees. Although granular application is more common than spraying, as a systemic pesticide, it ends up on the surface of plants that grow in chemically treated soil, indirectly affecting the beneficial non-target insects.

Generally, imidacloprid and bifenthrin are admixed to form the composition. The composition may be a solid or liquid composition according to the knowledge of the skilled artisan. Examples of suitable compositions include granules, dusts, powders, and wettable powders. Suitable liquids include emulsifiable concentrates, solutions, flowables, suspension concentrates and suspensions.

The amount of active ingredients in the composition of the invention can vary widely but is generally from about 0.1% to about 95% of active ingredient. (Percents are generally percent by weight in the current specification and claims of the present application unless otherwise denoted.) Preferably, the ratio of the amount of bifenthrin to the amount of imidacloprid products is from about 1:5 to about 4:6. The amount of bifenthrin and imidacloprid in a soluble concentrate formulation varies from about 2% to about 4% and from about 4 about 5%, respectively. The amount of bifenthrin and imidacloprid in granular formulations varies from about 0.1 to about 0.2% and from about 0.125 to about 0.25%, respectively.

 
 

Due to the effectiveness of diflubenzuron

The control of fly larval infestation is important in agricultural in order to avoid the illnesses and economic losses associated with such insect pest infestation. A method of controlling fly larval by direct application to the larval breeding medium is widely known in the industry. The method involves such direct utilization of the compound, N[[4-chlorophenyl)amino]carbonyl]-2,6-difluorobenzamide, sold under the tradename of DIMILIN® insecticide, a registered trademark of Duphar BV of Amsterdam, Holland (hereinafter referred to as diflubenzuron , the generally recognized generic chemical name).

Due to the effectiveness of diflubenzuron when used against fly larvae, the search for a more beneficial manner to control such fly larvae has spurred and continues to spur new research efforts. One attractive method for fly larvae control is to utilize diflubenzuron in feeds for controlling fly larvae in excreted feces. This method is commonly referred to as feed-through application. For instance diflubenzuron at levels of 0.5 to 1.0 mg/kg animal body weight, has been mixed directly into the feed of calves and dairy cattle and has shown effective control of house fly and face fly larval in the feces (R. W. Baker et al, J. Georgia Entomol. Soc., 11 (1976) 1: 67-71 and R. W. Miller, J. Economic Entomol. 67 (1974) 5: 697).

In addition to this direct feed addition method, diflubenzuron  has been encapsulated and tested for insecticidal activity, F. W. Knapp et al., Symp. Int. Meeting Controlled Release Soc. (Academic Press, 1980), as well as being applied in mineral blocks and delivered in a sustained-release bolus form (U.S. Pat. No. 4,166,107, issued to J. A. Miller et al on AUg. 28, 1979).

Procuring and cultivating a garden can be an excellent source of pride and provide a relaxing and rewarding hobby. However, pests such as the velvet bean caterpillar can ruin all the hard work by damaging the garden beyond repair. To control velvet bean caterpillars in the garden, all you need is the ability to follow a few steps and the patience to keep the control measures in place.

The present invention relates to novel compacted granular feed premix compositions containing diflubenzuron. These granular feed premix compositions provide enhanced larvicidal effectiveness and fly control of surprisingly low doses of diflubenzuron manufacturer .

It is an object of the present invention therefore to provide novel such compacted granular feed premix compositions with improved larvicidal effectivness and fly control.

It also is an object of the present invention to provide a method for preparing the novel compacted granular feed premix compositions of the invention.

These and further objects of the present invention will become more apparent by the more detailed description of the invention provided herein.

Place pheromone traps in the garden to capture the velvet bean caterpillar in its moth stage and control the population in your garden. See the Resources section for more information.
Check for the eggs of the velvet bean caterpillar on the underside of leaves and remove the eggs or the infected leaves. This is a difficult means of control because the eggs hatch usually within three days. Therefore, if you choose this measure of control, you need to check and clear the leaves every other day to properly control the velvet bean caterpillar.

The present invention relates to compacted granular feed premix compositions comprising, on a weight basis, about 0.5% to 84.0% diflubenzuron ; about 0% to 10% whole dried whey; about 0% to 2% water and the remainder of a compactable, insoluble carrier to total the composition of 100%.

Compactable, insoluble carriers suitable for use in the compositions of the present invention include clays and mineral salts, such as CaSO 4 , BaSO 4 or other mineral salts, CaCl 2 . The preferred carrier, however, is CaSO 4 dihydrate. Preferred compacted granular premix compositions of this invention have a granular particle size of 10 mesh to 100 mesh, with a particle size range of 20 mesh to 60 mesh being preferred.

This invention also relates to methods for the preparation of these compacted granular compositions. It unexpectedly has been discovered that compositions of the present invention, prepared by the compaction and granulation process of the invention, provide compositions which provide effective control of larvae when administering doses in animal feeds of diflubenzuron at rates as low as 0.025 mg/kg of animal body weight. Surprisingly, the compacted granulated compositions of the invention are more efficacious than diflubenzuron alone, the uncompacted composition or an alfalfa feed premix of diflubenzuron administered in animal feed for the feed through control of fly larvae and resulting fly control (see Table I). This invention also provides an improved method for controlling fly larvae and flies in the feces of animals. This is accomplished by orally administering, in an animal feedstuff or feed supplement, sufficient quantities of the present compositions to provide about 0.025 mg/kg to 10 mg/kg per animal per day of diflubenzurons .

Spray the garden with a chemical treatment of diflubenzuron. This chemical is for retail sale under the name Dimilin. This is a restricted use pesticide and for use with certified applicators only. See the resources section for more information.
Cultivate the ground underneath the plants regularly and check for the pupae of the velvet bean caterpillar. In the larval stage, the pupae caterpillar is brown and milky white in color.

 
 

 
 

source:townhall|diflubenzurons

Imidacloprid poisoning is rare and can be prevented

Imidacloprid , namely, 1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneam ine, is a systemic, chloro-nicotinyl insecticide with soil, seed and foliar uses for the control of sucking insects including rice hoppers, aphids, thrips, whiteflies, termites, turf insects, soil insects and beetles. It is most commonly used on rice, cereals, maize, potatoes, vegetables, sugar beets, fruits, cotton, hops or turfs, and is especially systemic when used as a seed or soil treatment.

Imidacloprid is a topical insecticide often used to prevent and treat flea infestation on dogs and cats. Imidacloprid is sold under various brand names by a veterinary office. A dog should see a veterinarian to be prescribed the proper dosage. Imidacloprid poisoning is rare and can be prevented.

U.S. Pat. No. 6,307,053 describes a process for the preparation of imidacloprids comprising reacting 2-nitroiminoimidazolidine with 2-chloro-5-chloromethyl pyridine in stoichiometric amounts in the presence of an alkali metal carbonate in an organic solvent under reflux condition. The alkali metal carbonate may be lithium, potassium or sodium carbonate. The organic solvent may be alcohols, ketones, acetonitrile or dimethyl formamide. Due to the alkali metal carbonates being not very soluble in the organic solvents, the solutions of the alkali carbonates are not easily flowable and pumpable, and the reaction mixture is not very homogenous so as to be easily stirred. Therefore, the above process is difficult to carry out. Besides, the filtrate containing imidacloprid obtained by the above process is concentrated by vacuum distillation. Due to the presence of unreacted alkali metal carbonates and their related salts in the filtrate resulting from use of alkali carbonates, there is bumping (flashing) turbulence during vacuum distillation of the filtrate, thereby rendering the process more difficult to carry out. Also, alkali metal carbonates have low basisity, thereby increasing the reaction time. The above process is described to be an improvement over the process of employing sodium hydride (NaH) in the place of alkali metal carbonate. Sodium hydride is a very hazardous reagent. Therefore, handling of the sodium hydride-based reaction is very difficult and cumbersome.

Indian Patent No 181755 describes a process for the preparation of imidacloprid manufacturer comprising, among other steps, condensation of 3-chloromethyl-6-chloropyridine with 2-nitroimino-1,3-dihydro imidazole in the presence of inorganic bases and ketonic solvents. The inorganic bases used may be carbonates or bicarbonates of sodium or potassium. The solvents may be acetone, methyl butyl ketone, methyl-t-butylketone or acetonitrile. The problems associated with the use of alkali carbonates in the above-referenced U.S. Pat. No. 6,307,053 are encountered in this process also.

Do not use on puppies less than seven weeks old. There are different dosages for dogs: less than 10 lbs.; 11 to 20 lbs.; 21 to 55 lbs.; more than 55 pounds.
Never apply to the skin, or the base of the neck to avoid a dog licking the medication. Never let the dog ingest the product.
Imidacloprid kills most fleas in about 12 hours and spreads over the skin oils of a dog and collects in the hair follicles, releasing the medication over the span of a month. Never give the dog more than one dosage a month.

According to the invention, there is provided a process for the preparation of the insecticide imidacloprid comprising reacting 2-chloro-5-chloromethyl pyridine with 2-nitroiminoimidazolidine with in the molar ratio 1:1 to 1:1.2 in the presence of an alkali metal hydroxide in an aprotic solvent at 45 to 60° C. under stirring.

It has been surprisingly found that the yield of imidacloprid is improved if the molar proportion of the 2-nitroiminoimidazolidine is marginally higher than that of 2-chloro-5-chloromethyl pyridine. Preferably, the reaction of 2-chloro-5-chloromethyl pyridine with 2-nitroiminoimidazolidine is carried out in the molar ratio 1:1.12 so as to improve the yield of imidacloprid .

If the dog licks the medication before it has spread and dry, look for drooling, twitching and muscle weakness. Consult a veterinarian if symptoms occur.
Never use on a dog that is hypersensitive to it. Avoid the eyes, nose and mouth of the dog. Do not use on pregnant dogs. Do not use imidacloprid with any other insecticides or flea medications.

 
 

 
 

source:townhall|imidacloprid

The way to use the glyphosate

The present invention relates to the field of agrochemical compositions and formulations. In particular, the present invention provides a composition comprising glyphosate and at least one taurate salt. The glyphosate and at least one taurate salt of the present invention can be advantageously mixed with the triazolinone herbicide and one or more aromatic solvent to produce compositions that are chemically and physically stable. The present invention is also directed to methods of making and using such compositions.

Glyphosate is an herbicide used to control and eradicate perennial weeds. It is sprayed in a diluted solution and metabolized by the weed, killing it. The first products on the market containing glyphosate were the Roundup lines. Now, several other brands market products containing glyphosate as an ingredient. Glyphosate products are used in both residential gardens and commercial agriculture. Some new crops have been genetically modified to be resistant to glyphosate so that it can be used to kill weeds without killing the cash crop itself. Glyphosates kills a wide variety of plant life including grasses, leafy and wood bearing plants and is found in herbicide products in varying amounts from 100-grams to over 600-grams per liter. Glysophate products come in either concentrated form designed to be mixed with water or pre-mixed for direct application.

To enable the efficient elimination or controlling of unwanted plants in agriculture and related endeavors, it is desirable to use effective chemical herbicides on these unwanted plants. Compositions containing multiple herbicides are desirable in agricultural and related endeavors due to broadening the spectrum or range of unwanted plant species killed or controlled and varying the onset of visual symptomology.

Due to the desirability of having a composition with the above mentioned properties, the combination of a triazolinone herbicide and glyphosate manufacturer has been disclosed in, for example, U.S. Pat. No. 5,935,905, U.S. Pat. No. 5,125,958, U.S. Pat. No. 6,127,318, PCT Publication WO 00/78139, PCT Publication WO 02/063955 and PCT Publication WO 01/70024. The combination of a triazolinone herbicide and glyphosate salt has been thought to exhibit a herbicidal effect against a very broad spectrum of unwanted plant species and a triazolinone herbicide is known to have fast onset of herbicidal activity as seen from visual symptomology, while glyphosate salt is considered to be slower with onset occurring just after typical triazolinone herbicides. This has the potential to be a very effective combination. However, a problem in the art of formulating the triazolinone herbicide and glyphosate salt mixture is in successfully achieving both chemical and physical stability in the composition over significant periods of time.

In general, a relatively small amount of the triazolinone herbicide has been used in conjunction with glyphosate. Chemical stability is most important in this type of composition to ensure the small amount of the triazolinone herbicide is fully effective. Typically, less than one percent is used commercially to keep the cost of the composition low, while still yielding spectrum and onset of visual symptomology benefits. Examples of problematic chemical degradation include hydrolysis, oxidation, dehalogenation and bond cleavage. The chemical and physical stability of a glyphosate and triazolinone herbicide composition is a key objective in the art.

Wear garden gloves and face mask to handle glyphosate products. Determine the dilution measurements according to the directions on the packaging of your particular product.
Pour measured glyphosate product and water into a spray bottle or pump sprayer. Close the lid securely and swirl repeatedly to combine the mixture.
Spray the glyphosate solution directly onto the weeds and any other plants that you wish to eradicate. Do not soak the surrounding soil with solution as it may impair your ability to replant the area.

The present invention provides new herbicide compositions that have superior chemical and physical stability, broad herbicidal spectrum effects and very good balance of onset of visual symptomology.

Specifically, the present invention is directed to a composition comprising glyphosate and at least one taurate salt. This composition can further comprise: (i) a water-immiscible phase comprising a triazolinone herbicide and one or more aromatic solvents with (ii) an aqueous phase comprising the glyphosate and an emulsifier comprising the at least one taurate salt. The triazolinone herbicide and glyphosate can be present, at least collectively, in a herbicidally effective amount.

The present invention is also directed to methods of making and using the compositions of the present invention.

 
 

 
 

source:townhall|glyphosate

How does Fipronil work?

The present invention relates to a novel crystalline modification of fipronil, to a process for the preparation of the same, to pesticidal and parasiticidal mixtures and compositions comprising said crystalline modification and to their use for combating pests and parasites.

Fipronil (formula I) is an active compound for controlling certain insect and acarid pests, and parasites.

Various processes for the preparation of fipronil have been described, generally and in detail. Documents which give detailed preparation procedures are e.g. EP 295 117; EP 460 940; EP 484 165; EP 668 269; EP 967 206; EP 1 331 222; EP 1 374 061; U.S. Pat. No. 5,631,381; CN 1374298; or J. of Heibei University of Science and Technology, Vol. 25 (2), Sum 69 (2004), Dok. Serial No. 1008-1542 (2004) 02-0018-03.
Fipronil is an insecticide that has been registered for use by the EPA in the U.S. since 1996. It is used to ward off fleas, ticks and other insects.

Characterization of the fipronil material obtained by the processes described in the prior art is usually done by 1H-NMR analysis and/or measurement of the melting point. The described melting points are in the range of from 187° C. to 203° C., mostly in the range of from 195° C. to 203° C. In the Pesticidal Manual, 13th Edition (2003), British Crop Protection Council, p. 433, fipronil manufacturer  is described as a white solid with a melting point of 200 to 201° C., with technical fipronil having a melting point of 195.5° C. to 203° C. Observations of different crystalline forms of fipronil have not been described, let alone any characterization of a certain crystalline modification or a preparation procedure for obtaining a certain crystalline modification.

Fipronil stops regular nerve function by blocking gamma-aminobutyric acid receptors in the central nervous system. This GABA receptor neural system helps prevent over-stimulation of the nerves by blocking some neural activity. When Frontline containing Fipronil is applied topically to your cat, it is stored under your cat's skin in the oil glands. This makes Frontline waterproof as it continuously releases the Fipronil through your cat's hair follicles.

For the large-scale preparation and formulation of a market compound such as fipronil, it is of crucial importance to know whether different crystalline modifications (also frequently referred to as polymorphs) of a compound exist, how they can be obtained, and what their characteristic properties are. Crystalline modifications of one compound may have very different properties, for example with regard to solubility, rate of dissolution, suspension stability, stability during grinding, vapour pressure, optical and mechanical properties, hygroscopicity, crystal size, filtration properties, desiccation, density, melting point, degradation stability, stability against phase transformation into other crystalline modifications, colour, and even chemical reactivity.

Common adverse reactions in cats from Frontline containing Fipronil, are chemical burns to the site where the topical was applied, hair loss, lethargy, behaviors such as running in circles, hiding, agitation, crying and excessive grooming.

For example, different crystalline modifications frequently manifest themselves in different forms of the crystals, such as needles or plates. This is of relevance for e.g a leading to loss of time and being needles can have significantly different bulk densities which has implications for storage and packaging. Another the powder which can produce hazardous dusts, or as dust-free larger crystals. Different modifications of fipronils  have different essentially excluding other crystalline modification forms (i.e. in over 80% by weight). This ensures reproducibility and stability in all aspects of the production, transportation, storage and use of the corresponding solid state form.

Accordingly, a novel crystalline modification of fipronil, a process for its preparation, pesticidal and parasiticidal mixtures and compositions comprising it and its use for combating pests and parasites has been found. The novel crystalline modification of fipronil is defined as "novel crystalline modification V" throughout this application.

Also, most surprisingly, 3 other crystalline modifications of fipronil have been found, which are subject to co-pending patent applications. Especially surprising was that the present crystalline modification V of fipronil has a very similar melting point as a second crystalline modification I, both melting points lying in the range of the melting points given in the prior art (i.e. 195 to 203° C.). Moreover, two further crystalline modifications II and IV of fipronil chemical , as described in co-pending applications, undergo phase transformations during heating into the more stable forms I and V, and thus in a typical melting point measurement will give the melting points of these forms I and V. The solid forms of fipronil thus are part of a very complex crystallization scenario. It can be concluded that the melting points given in the literature in no way can indicate which crystalline modification or crystalline modification mixtures were analyzed.

In T 605/02, the Technical Board of Appeal of the European Patent Authority ruled that, in the absence of a respective described preparation procedure, even the XRD pattern of a certain crystalline modification does not constitute prior art for lack of enablement. Thus, melting points given in documents published prior to the filing of this application cannot be regarded as prior art for the present invention as they do not enable the artisan to prepare the novel crystalline modification of fipronil .

 
 

 
 

source:townhall|fipronil